TWI232174B - A film of yttrla-alumina complex oxide, a method of producing the same, a sprayed film, a corrosion resistant member, and a member effective for reducing particle generation - Google Patents

Abstract

An object of the invention is to provide a film of an yttria-alumina complex oxide having a high peel strength of the film to a substrate. A mixed powder of powdery materials of yttria and alumina is sprayed on a substrate to form a sprayed film made of an yttria-alumina complex oxide. Preferably, the powdery material of yttria has a 50 percent mean particle diameter of not smaller than 0.1 mum and not larger than 100 mum, and the powdery material of alumina has a 50 percent mean particle diameter of not smaller than 0.1 mum and not larger than 100 mum. Preferably, the yttria-alumina complex oxide contains at least garnet phase, and may further contain perovskite phase.

Description

1232174

[Technical field to which the invention belongs] & The present invention relates to an yttrium oxide-alumina composite oxide ===, an oxide-oxidized composite oxide film, a dazzling film member and a low particle member. Corrosion resistance of plutonium [prior art] In a semiconductor manufacturing device that is in a state of cleanliness that requires a clean state, the deposition gas is used for deposition: two gases, and a cleaning gas, which uses a gaseous gas and a gaseous gas: Letters of rotten name sex gas. For example, in thermal CVD

Semiconductor clean gas made of corrosive lice. In this gas IK :! stage, WF6 AH, 12 and other rotten holes are also used as the gas for film formation. Anti-shore ί 2] PVD film formation step, or last name engraving step 'with chemical iiέ' ΐ 副 by-products will be deposited on the crystal seat, electrode, tread: m is generally called the "cold wall" t case Since the degree of cavity wall surface is relatively low, although the accumulation in the cavity wall can be used at an appropriate time, it is easy to use. Such sediments, such as sediments, have increased; = = ΐ cleaned, but adverse conditions such as rate occurred. Will result in process changes or reductions

The ancient and earthy methods to prevent such powder particles from falling are known as blast processing such as bead guarding or glass beads on metal plates. The surface is made rough Ways to improve retention.

7066-4891-PF (N); Tcshiau.ptd Page 5 1232174 V. Description of the invention (2) [Summary of the invention [issue = problem to be solved] Component for a wide-cavity manufacturing device (eg, housed in the device High resistance to ^^, and ^, the top / formation of the halogen gas or its plasma tool is contained in the installation, λ s private state of the coating. In addition, when applied in this case: deposition on the inner wall of the mf cavity When writing the by-products, it was revealed that by the description of the temple wish _'110136 俾 can be suppressed and: r has a relatively large 'Γ' point for the self-gathering of the gas. That is, ρ & amp ^ ^, Even in this film, the following problems will occur. This may cause cracks and cracks on the film. If this kind of powder particles appear in the film, it will reduce the relative ease. The product comes off from the substrate, and "two :: r = :: r" is not a good choice. The problem of the present invention is to provide a low-particle component that can be used stably for a long time. Seed deposits Retention force 'Furthermore, the problem of the present invention is to hold on the surface', and it is not easy to produce the retention force. Low particles with less equipment maintenance warranty time; fine powder caused by materials ’[means to solve the problem].

7066-4891-PF (N); Tcshiau.ptd Page 6 1232174 V. Explanation of the invention (3) The invention of the first aspect is related to the method of dissolving yttrium oxide powder and alumina powder, and mixing the powder onto the substrate, and Method for forming a thermal spray film composed of yttrium oxide-alumina composite oxide. Furthermore, the present invention is an oxide-oxidized composite oxide film obtained by the above method. In addition, the yttrium oxide-alumina composite oxide film of the present invention comprises the oxide of a stone-stone phase-alumina composite oxide, and the yttrium oxide-alumina composite oxide of a perovskite phase, and The ratio of the peak intensity yal (420) of the (420) plane of the perovskite phase to the peak intensity YAG (42〇) of the (420) plane of the garnet phase obtained by χ-ray diffraction measurement. YAL (42〇) / YAG (42) is 0.05 or more and ι · 5 or less. Furthermore, the spray film made of the yttrium oxide-alumina composite oxide of the present invention is free of cracks having a length of 3 Am or more and a width of 0.1 or more. Furthermore, the present invention includes a money-resistant member including a substrate and an yttrium oxide-alumina composite oxide film, wherein the yttrium oxide-alumina composite oxide is an yttrium oxide-alumina composite oxide containing an f-garnet phase. Yttrium oxide-alumina composite oxide with perovskite phase, and measured by X-ray diffraction measurement, the peak intensity of the (420) plane of the Jochenite phase is YAL (42〇), which is the same as that of the garnet phase. The ratio yal (42〇) / yag (42〇) of the peak intensity YAG (42〇) of the (420) plane is 0.05 or more and 1.5 or less. Furthermore, the present invention is provided with a corrosion-resistant member having a substrate and a thermal spray film, wherein the thermal spray film is made of yttrium oxide-alumina composite oxide, has a length of 3 // m or more, and a width of 0 · ι Above the crackers.

V. Description of the invention (4) Furthermore, the second aspect of the invention is a low-granularity structure, and the following formula shows that the product ratio α of the base body and the upper surface layer of the base body is 50 or more, and the weight is 700 kg. The surface of the different average unit area «= (Table according to the adsorption method .... (cm)) X (overall density of the surface layer (cm2 / g)) χ (thickness of the surface layer invented by the inventor) The composite powder is sprayed on the substrate, and the shape is a thermal spray film composed of a mixture of yttrium powder and alumina powder. Results ^ f The film with high peel strength was oxidized by yttrium oxide-alumina composite. ^ Now stable formation of the substrate is better than in the pull obtained in this way, and no significant turtle yttrium-alumina composite oxide film is found even when it comes into contact with corrosive substances ^ The peeling strength of the substrate is also high In addition, when the film is subjected to heat treatment: ί produces peeling or powder particles. The peeling strength of this body, even in the "::::" enhances the membrane to the substrate, and successfully found that the widget can be processed afterwards. The surface area ratio of this component is improved. . By the invention of the deposit, the invention of maintaining the two-state plutonium, which can reduce the deposition stress, can be manufactured with the predetermined "::: ^" in the second preferred state, the average particle size of the oxidized period is " // m and below 100 ％. In this way, u · i is modified :: rot = substance (the gaseous polymerization of the system) and more, 'the viewpoint of improving the adhesion of the film to the substrate more In terms of, 1232174 " " 丨 _ 丨 __— 15. Description of the Invention (5) The average particle size of 50% of the oxidized powder is preferably above 0.5, especially above 3 # m. In addition, from the viewpoint of further improving the adhesion of the film to the substrate, the 50% average particle diameter of the yttrium oxide powder is preferably 80 or more, more preferably 50 0 or less, and more preferably # m or less is more preferred. In a preferred embodiment, 50% of the alumina powder has an average particle size of 2 'and 10' or less. By this, cracking can be more suppressed :: 〇1, 1 improves the Corrosion resistance of corrosive substances (such as halogen-based gas plasma). More child-friendly i: From the viewpoint of further improving the adhesion of the film to the substrate, t, 50% of the emulsified aluminum powder is flat. The average particle diameter is preferably at least 0.3 m, particularly preferably at least m. In addition, ^ ^ ^ ^ ^ ^ ^ ^ In 3 // ^ ^, you can improve the adhesion of the film to the substrate: the average particle size of 50% of the oxide powder is preferably 8 ", especially the following, It is more preferable to be below 1 () _. Not existent: two == rr… 5 °% average particle size ⑽), when the secondary particles exist, the "more-secondary particle size" , But when there are 6 conditions, it is the particle size of the secondary particles. However, there is no particular limitation on the ratio of the oxidized particles. However, it may contain oxidized powder and oxidized powder with-alumina complex oxygen: bismuth. The third component of the lambda type is preferably a stone plum stone phase that does not cause any adverse effect on the yttrium oxide described later; the stone phase and the crystal phase of the material phase; Qin; Zizi! Yu compound in the oxidative mind-oxidizing inscription. In this type of mineral phase, shell blades such as yttrium oxide or strontium oxide are replaced as shown below. Page 9 7066-4891-PF (N); Tcshiau.ptd 1232174 V. Description of the invention (6)

La2 03, Pr2 03, Nd2 03, Sm2 03, Eu2 03, Gd2 03, Tb2 03, 〜〇3, Ho2〇3, Er2 03, Tm2 03, Yb2 03, La2 03, MgO, CaO,

Sr0, Zr02, Ce02, Si02, Fe2 03, B2 03. When spraying the mixed powder, the mixed powder can be directly sprayed. Alternatively, a mixed agent and a solvent may be added to the mixed powder, and the powder may be granulated by spray-drying to spray-granulate the powder. When spraying the mixed powder, it is best to perform the spraying at a low pressure. The pressure is preferably less than 100 T ○ r r. Thereby, the pores of the dissolution film can be further reduced, and the money resistance of the final film can be further improved. In a preferred embodiment, the heat-spraying film can be heat-treated, thereby further improving the peeling strength of the film from the substrate. The heat treatment temperature is preferably 13,000. It is considered that if the heat treatment temperature reaches the peeling strength between the body material and the corrosion-resistant film material. Above C, especially above 1400 and reaching 1 3 0 ° C, it will be easier to generate the reaction layer, and as a result, the body of the film will be improved; ==== special restrictions, as long as it does not make the tip >,, can be served, from this point of view, the most cup below y-onnn. If the heat treatment temperature of the thermal spray film is increased, the temperature is near the reaction layer formed; the production temperature is the highest: 180 °. . . the following. In addition, from the viewpoint of heat treatment suppression, it is best to be 1700. (: The following.) The film system of the present invention that has cracks can continuously exist on the surface of the substrate. It must be formed continuously across the entire surface of a predetermined surface of the substrate. For example: including J: not

1232174 V. Description of the invention (7) = base if: the discontinuity on the surface, or the formation of multiple island-like layers: 膑 also includes the existence of dots or dispersion on the predetermined surface of the substrate. In the embodiment, the film system of the present invention is substantially non-cracked, and particularly refers to a film having no length of 3 "m or more and two kinds of official cracks. It is possible to use a film with a crack of more than 7111. This 1 Z ...: I used a tracing type electron microscope to confirm the sacrifice film at 1000 times the chemical conversion rate. The material of the substrate is 4i ¢.) ΛΑ iro J. »I ’m crying for electricity 1: Two: Ϊ system. But '· It does not contain any bad words that may be produced in the process of Dian Sui Jie, preferably: aluminum or aluminum nitride, oxidation; 2 ^ This complex point or solid solution, thorium oxide, Oxygen sheep, Lu, and rolled yttrium. The peeling strength of the matrix of emulsified yttrium and yttrium yttrium compound or solid solution film is rooted, and the diameter is set to a diameter of φ 5 · 2mm. The facing substrate can also be porous. In addition, the surface roughness Ra can be more than 1 // m, the surface of the soil body The center line average outer Table 1 billion can improve adhesion to the substrate film, and · 2 "m or more. This can be a phenomenon. Inhibition of powder formation due to film peeling Yttrium oxide-alumina composite oxide For example, the following can be selected. There is no particular limitation on Lichia, (1) Y3Al5012 (YAG: 3Y2〇3 · 5A1 〇λ contains the structure of the oxidized period and the oxidized name is 3 · 5 2 3. It has a "rate" and has a garnet knot (2) YA103 (YAL: Y203. A1 〇λ 2 3). The crystal structure of titanium ore.

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〇) Υ4Α 12 02 (ΥΑΜ ·· 2Υ2〇3 · ai2o3). Monoclinic system. In a preferred embodiment of the villain, the yttrium oxide-alumina composite oxide film contains at least a garnet phase. In a preferred embodiment, the yttrium oxide-aluminum oxide composite oxide film contains a garnet phase and a perovskite phase. In this case, the peeling strength of the film to the substrate can be further improved, and cracks are less likely to occur. Particularly preferred is a yttrium oxide-alumina composite oxide containing a garnet phase and a perovskite phase, and the peak intensity YAL (420) of the (42) plane of the perovskite phase obtained by X-ray diffraction measurement, The ratio (YAL (420) / YAG (420)) to the peak intensity YAG (420) of the (420) plane of the garnet phase is 0.05 or more and 1.5 or less. (YAL (420) / YAG (420)) is particularly preferred if it is 0.05 or more, or particularly preferred if it is 0.5 or less. The film of the present invention and the laminated body between the film and the substrate have excellent corrosion resistance, and particularly have high corrosion resistance to the _ series gas and the _ series gas plasma. The object which exerts the corrosion resistance of the residual component of the present invention There are semiconductor manufacturing equipment such as thermal CVD equipment. In such a semiconductor manufacturing apparatus, a semiconductor clean gas composed of a tooth gas plasma is used. The money-resistant member of the present invention has corrosion resistance not only in a halogen gas plasma, but also in a plasma environment in which a tooth gas and an oxygen gas are mixed. This "quot" halogen gas can be exemplified as: C1F3, NF3, CF4, WF6, BC1, etc. Furthermore, the second aspect of the invention is to provide a low-granular component, which includes: a substrate, and a low surface layer on the substrate. Granular components and average unit area

7066-4891-PF (N); Tcshiau.ptd

1232174 V. Description of the invention (9) The surface area ratio α is 50 or more and 700 or less. According to such a low particle component, when the powder is deposited on the surface of the low particle component = it is held in the pores of the surface layer ', and it is not easy to drop the fruit from the surface layer. Falling or flying away can reduce the amount of time spent cleaning the sediment. The surface area ratio of the average unit area is defined according to the following formula. The surface area ratio of the oxygen adsorption method (cmVg) x ((cm)) X (overall surface layer density (g / cm3)). The average unit area of the layer is a kind of clothes return bar buckle. This surface area value can be calculated, for example. In detail, it means that the surface layer when the surface state of the surface layer is smooth when the surface layer is not considered: front = lower Surface area: The surface area ratio (cmVg) according to the lice adsorption method means (the surface area ratio of flat denier). ~, The surface layer is lower than the average unit weight. In addition, if: H, the degree of fine pores. Bu right multiplies the thickness of the surface layer (cm) by the surface layer, the surface area ratio of her decent layer, the weight of the surface in the early stage (cm2 / g)), and multiplies it by the table (the average unit surface weight of the surface area borrowed by the table (g / cm2)), the surface area ratio (以 2 / 以 2) of the product of f can be calculated. The attached force is the degree to which gas is absorbed by 'in an area of 1 cm2 in m. The so-called overall density refers to the weight divided. In addition, Bury I shows a body with lice holes and closed pores with a 3 7066-4891-PF (N); Tcshiau.ptd 1232174

5. Description of the invention (10) Product density. The surface area adhered from this point of view by holding such an average meter on the surface of the substrate on the surface layer will also be thick. In addition, because of the holding force of the surface layer, see Table 3. Table 4)

In the early stage of S5, open the air, reduce the product, and the layers will change. In the present invention, α must be set to 50 or more. The surface area ratio α of the area belongs to a large surface layer, so that by-products and particles can be adsorbed, adhered, and pores, and the particles can be prevented from falling or scattering. It is more preferable to set α to 100 or more. When α is small, even if the amount of by-products is the same, the on-surface result will cause the by-products to fall more easily. The seedling nail effect will be smaller, so the by-products will be smaller. α 5 0 or more is significantly larger than the case of general polishing and trimming using sputtering (comparative examples C 1 and c 2 described later). This is considered to be because the table of average unit area of the surface layer is even larger. = Becomes larger, the surface area of the appendices or by-products should be taken as a matter of course = :: This should have advantages in terms of preventing powder particles from falling or scattering. In general, if the average unit area is The surface area ratio α is more than 700. It is known that it will cause the fine powder to fall and increase the amount of dispersion. This is because-: ϊ Ϊ700 'When the thermal cycle is applied to the surface layer, the surface is wide: ceramic ... will appear Microscopic damage, on the contrary, becomes the source of fine powder. From this point of view, α is preferably less than 50,000 ', especially less than 300. The open porosity of the surface layer is preferably 10% by volume and more preferably% by volume. .This can promote the surface layer above, especially the storage of 15 products or fine powder.

1232174 V Description of the invention (11) The more 30 vol%, the better, the open porosity of table @ \\ is below 3Q vol%. If the overshoot will be reduced, ^ Λ / Λ will be reduced, and the mechanically generated tortoise list s itself will become a dust generation source, which will also increase the amount of fine powder. The surface porosity (open porosity, closed porosity / closed porosity) is preferably 10 or more. The ratio of the ratios (maintaining adsorption of open pores or micropowders will be caused by two = no by-products 0.05 to 5. _. By using this: two ": pore size or micropowder to maintain open pores in open porosity: ... Promote the by-products further, 'If you look at it from another point of view, the design specifications of a device are the same :: It is better to be the same as the manufacturer. The reason why Tian Kongzheng is better than 0.05 is because The micro-ditch that is formed is said to be stored and moved under atmospheric pressure. == Π 时 依 ～ 〜1 ~ or moisture. When this wafer is supplied to ㈣ or into the mouth :; in the case of Qiaoqu, it is Make sure that the edited w is made, and the $ a, 隹 彳-@ ~ that are adsorbed in the next step of the woolen fabric will be finely grooved.

τ corpse / r and attached components are degassed. Process chamber layout (exhaust pipe size or gas flow mode), &OK;. ㈡ :: Fang 々, she "%-丄 heart. On behalf of the subtle grooves; dyslexia < million styles of designers is a normal situation. The design specifications of the micro-ditch index have the same degree: if the film surface is left empty, it will not cause any damage to the manufacturing process. Γ: ί 本: Γ

V. Description of the invention (12) Outside 'Because of the common point of view, the area is greater than the wafer area', so the total surface area, but the most: the pore diameter can be the same as the design specifications. From the viewpoint of keeping adsorption of the product or fine powder, it is preferable. Above 50, especially with 00 or more as the micron = green surface, the peeling strength of the substrate is reduced to the following, especially the thickness of the layer is best set under __, 钲 2: material, for the purpose The premise of having the required corrosion resistance is double: self-made. In a preferred embodiment, the material of the surface layer may be a compound of a rare earth tritium oxide, an alkaline earth oxide, a reverse compound, a chaotic compound, a gaseous compound, a chloride, an alloy, such solid solutions, and In a group of & objects. More specifically, it can be exemplified as follows. Cyanite (cordierite), diamond, silicon nitride, aluminum nitride, chemical town, fluorinated light, fluorinated. The name of the ocherite mineral has a theoretical composition of 2Mg〇-2Al2〇3-5Si〇2, but may also include a solid Fe component or an alkali component. Strictly speaking, although it is the name of the low-temperature phase of this composition, it is usually high, σ 2: it is called ocherite. Here, mainly composed of Dong Qingshi, the two eriocyanite series has excellent corrosion resistance because it contains Mg〇 in the composition. At the same time, if talc is used as the MgO source (mineral name, 3Mg〇_4Si〇2_H 〇) , Because the talc liquefied during the heat treatment will move around the ^ ^

1232174 Description of the invention ⑽-^ ~ ----- In the pores: Therefore, the shape of talc becomes pores. By selecting the particle size of talc or the conditions of heat treatment, the α value can be controlled within an appropriate range. Diamonds are mainly formed on the surface by the CVD method. Because the diamond itself has a pyramidal or cuboid shape, you can choose the value by controlling its own step size: size. In addition, even if a metal element such as Si is mixed in the film in advance, and then a fluorine-based plasma such as NFg is used to remove only the metal element by etching, the α value can be controlled. In the case of diamond, the substrate is printed with silicon nitride, aluminum nitride, silicon, carbon, and aluminum oxide. It is also possible to form a surface pore structure of silicon nitride. For example, if a silicon nitride sintered body with y 〇 and Al 2 O 3 as a sintering aid is heat-treated in a gas system such as cF4 + 〇 2 Xu Zhong 'according to 100 ~ 3 0 0 ° C, because only By choosing the remaining nitride nitride, you can obtain a fine oxide composed of Y2〇3-Al2〇3-Si〇2 series oxide, or X-rat Y-A 1-S i-N-0 series oxide. Hole structure. Alternatively,% of heat treatment is performed in a 30 ° C molten alkali with KOH: NaOH = 1: l (mol ratio). Because the grain boundary phase can be selected for dissolution, a pore structure with silicon nitride as a soil can be obtained. . As described above, the pore structure of the present case can be formed not only by the thermal spray method, but also by the gel method, PVD, CVD, or precipitation from a solution. Alternatively, it is also possible to form a pore structure near the surface layer by performing an etching treatment on the surface chips # > t w. ^ 9. A particularly preferred embodiment is a surface layer composed of a yttrium-containing compound. Such compounds are preferably such as: yttrium oxide, solid solution containing yttrium oxide

Compound oxide of yttrium, yttrium trifluoride. Specifically, for example, a yttrium oxide, a zirconium-yttrium oxide solid melt, a rare earth oxide-yttrium oxide solid body,

7066-489l-PF (N); Tcshiau.ptd Page 17 V. Description of the invention (14) A12〇3, 2Y9〇q 3Υ2〇3, YF3, Y ~ A1-(〇) —F, Y2Zr207, y ai2 03 ° 2 is more preferably a surface layer composed of a mixed powder obtained by dissolving a mixed powder onto a substrate, and a shaped powder of B and an alumina powder. Therefore, the oxygen 9 shells described in the invention of the yttrium-alumina composite embodiment of this surface layer can be directly transferred to the above-mentioned second film. [The oxide composite oxide is preferably 50% of yttrium oxide powder and 100 / m or less, 50% of alumina powder on average: 1 or more and 100 / ζπ! Or less, and the heat-treated film has been heat-treated. Trail Z. Above 0.1, the yttrium oxide-alumina composite oxide film contains at least " except, preferably, the yttrium oxide-alumina composite oxide film contains two stones. The better one is the X-ray and radiographic measurements of the perovskite phase (peak titanium broad phase YAU420 of 4) and the (420) plane beep value intensity ratio YAL (420) / YAG (420) of the garnet phase. ) Above 0.05 and j 5 degrees ^ (. 42〇) When the low particle member is to be exposed to a corrosion-resistant substance, the material that can be corrupted can be exemplified as follows. π compounds, oxygen, gas, boron chloride, chf3, cif3, SFe, Nf3, HBr, TiCl, WF6, SiCl4, hydrogen, and these mixed gases. The carrier gas may be mixed with He, N2, and Ar. In the present invention, the substrate material may have a lower corrosion resistance to corrosive substances than the surface layer material. The needle is pointed obliquely. As shown in Fig. 1 (a), the low particle member i has a surface layer 3 formed on the surface 2a of the substrate 2. From the surface layer 3 surface 3a toward the base page 18 7066-4891.PF (N); Teshiau.ptd 1232174 V. Description of the invention (15) The body 2 surface 2a communicates with the open porosity of the body 2. : The inner wall surface of the open pores'2b is a base pore diameter. Because: 3: =:: 1 The pores 4 are as described above with a smaller depth. The illusion is: a certain degree of thickness' so it has a slenderness (width i (b), which means that if it is a wide-touch material, then it ’s For example, before the Rotten Margin Γ was only / 1 'and formed a solid line state. The dotted line is the surface 7 a of the inner layer 7 of the open air hole 6 suffered 1 rot, even in beans, # 料 盆 μ The exposed surface 2b will also be subject to corrosion. (Comparative volume ratio μ is shown as number 8 of the surface layer 7 engraving rate, which will be relatively relatively generated from the surface 2a of the substrate 2 as the front end of the component. However, This hole 8 is connected to the open air hole 6 r, "; the relative etch rate of the inner wall surface 6 a of the open air hole 6 is the result of the relative etch rate. . This pair inhibits the structure that is almost unchanged from the code, but will become larger (which has a more advantageous structure. Gu Zhuwen corrodes the dust of the substrate 2 to produce the material of the upper substrate # | 〇 * For the production process in the plasma container: Restriction. However, it is better not to contain elements that may be said, and it is better to be Lv or nitriding in Lv. / In this regard, the compound or solid body, oxygen _ \ Emulsified Shao, oxidation 1 Lu and the oxidized age of the incarnation. In a particularly good implementation ίΐΓ skimmer and oxidized age compounds or solidified yttrium oxide ~ IUb &# ^ In the complaint, the base system consists of alumina, spinel, In a preferred embodiment, after the formation of the surface layer, the surface layer is formed by combining the emulsion, the complex, or the composite oxide.

7066-4891-PF (N); Tcshiau. Ptd page 19 1232174 V. Description of the invention (16) Applying a compressive stress layer generates dust. Control surface other restrictions. The most suitable powder shines in heat treatment. The above-mentioned changes, so that the volume of the film can be further increased as the film is re-applied. The other method of the present inventor's is that it should be machined, and this method can be like heat treatment. In this way, it is possible to suppress the heat shrinkage of the volume from the surface layer as well as the mixed powder on the former substrate. The result is that the method can be used to describe the α unit, which will cause changes in the final cause. The phenomenon will be exemplified. For example, the method of increasing the surface area ratio α of the sexual rot I value does not have a mixed film of special oxidation age powder and alumina powder. Secondly, the melt spray film is subjected to a reaction during dissolution and the volume will be generated. Most air holes. Then, the phase transition of the crystalline phase is performed again, and the pores are increased to increase the value of α. In this case, an acid solution or a plasma etching treatment is used. Even if you use the advanced plus control. [Embodiment] (Experiment A) Zu & A. Each element having an average particle diameter (50% average particle diameter) shown in Table 1 was prepared. Among the average particle diameters shown in Table 1, the average particle diameters of 2 · 5, 5 " m and each of the yttrium oxide particles (for example: AAB A3) belong to

Human granules, other oxide particles (such as: A 4 ~ A 8), the average particle size is 9 shells; I belongs to two: under particle size. In addition, the average particle diameters of 0.1 a / m, 0.3 # m, 4 // m, and fm alumina particles (such as A1 ~ A4) belong to the primary particle size, and other alumina particles (such as: A5 ~ A8) The average particle size is a secondary particle size. In Examples A1 to A8 of Table 1, the yttrium oxide particles and the alumina particles are weighted.

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V. Description of the invention (17) Amount ratio 57.1: 4 2 · 9 ratio is mixed. The molar ratio of yttrium oxide to alumina is 3 ·· 5. In Examples A1 to 3, yttrium oxide powder and alumina powder were wet-mixed by a ball mill and granulated by a spray dryer to select particles having an average particle diameter of 40 // m. In Examples A4 to A8, yttrium oxide powder and alumina powder were dry-mixed. '

A substrate (alumina purity of 99.7%) made of flat alumina having a size of 50 × 50 × 2 and a thickness of 2 mm was prepared. A plasma dissolver manufactured by Sulcemic Corporation (company name, transliteration) was used to electrolyze the mixed powder onto the substrate. During dissolution, argon flows at a flow rate of 40 liters / minute, and hydrogen flows at a flow rate of 12 liters / minute. The dissolution shot output is set to 40 kW, and the dissolution shot distance is set to 120 μm. In Example A9, only the oxide-alumina garnet powder (average particle size 40 # m) was plasma-sprayed onto the substrate under the above conditions. The obtained films were subjected to the following measurements. (Identification of Crystal Phase) The crystal phase was identified using an X-ray diffraction device. Therefore, Y A L (4 2 0) / Y A G (4 2 0) is calculated. The measurement conditions are shown below.

CuK a, 50kV, 300mA, 20 = 20-70. Rigaku Electric

Device used: Rotary paired cathode type X-ray diffraction device "RINT" manufactured by the company. (Peel strength) Measured as shown below. 1. The size of the sample (layered body) after film formation is 2 mm (including film thickness).

1232174 V. Description of the invention (18) 2 · The cutting sample shall be made of Cingjing. Order 5 knives for ultrasonic washing 3. Prepare A1 tack with bulking agent (Transliteration). This adhesion area is shaped by a bismuth piece from Nika Corporation (company 4. A tack is adhered to the film-forming surface. Y Straight φ 5.2 mm in a circular shape. 5 • The stud with the sample is strong and upward Pull until the film is peeled off. From the tool, calculate the peel strength using the self-tester (peel strength = peeling load and adhesion area at the time of peeling), it will be peeled off at the adhesive part = weight / big Nail adhesion area). The value of this formula (with or without cracks) is regarded as the measured value. It is robust in the I-resistant test device-implemented. In C12 gas (closed: the sample of each case, and the next Conditional gas flow is 30 0ccm. Carrying: Two devices 1 hold each sample for 2 hours. C12 body pressure is set to 0 · 1 torr, and the gas flow (argon) is 100 sccm. Gas output. For each sample, measure Qi Weight change after applying + 0㈣, bias voltage 31 ° W. * Respective weight before and after the test, and calculate

7066-4891-PF (N); Tcshiau.ptd Page 22 1232174 V. Description of the invention (19) The average particle size of Ya 2 03 powder (^ m) The average particle size of Al 2 0 3 powder (fim) Peak-intensity ratio YAL (420) / YAG (420) Peel strength MPa Cracking resistance test Weight increase mg / hr Other A1 0.1 0.1 I 0.000 8 Μ 、, 0.0 0.0 A2 0.5 03 0.597 12 Μ 0.0 A3 5 4 0.324 30 Μ 0.0 A4 20 20 0.203 10 Μ 0.0 A5 50 50 0.108 12 Μ 0.1 A6 80 80 0.07 11 Μ y \ ι \ 0.1 A7 100 100 0.05 10 Μ 0.1 YAM phase A8 120 120 13 Μ 0.7 A9 YAG powder only (40 μηη) 0.00 3 Youbu 12 was sprayed on the substrate from the end, and no perovskite phase was found in the spray film. However, the peel strength was relatively low, cracks were found, and the weight increased after the corrosion resistance test. The mixed powder was spray-sprayed in A1 to A8, and its peeling strength was large, and no crack was found. In particular, if the particle size of yttrium oxide powder is set to 0 / core 100_, and the particle size of oxidized oxide powder is set to 0_3 ~~ 100__ = special = strength will be above 10 MPa 'and no cracks are observed, ❹ The particle size of the 'oxidation record powder and the oxide powder in ΑΑ8 is ， =, sub Λ ΑM phase. In Δδ, although the peel strength is set to be comparative (the second one, it will be found that the money resistance will be slightly reduced. For each of the examples A1 to A9, the heat treatment is performed in the atmosphere when the frost silk is small. 3 Experiment A The same evaluation, moxibustion was performed on the membrane of each case, and the results were as shown in Table 2.

1232174 Five 'invention description (20) [Table 2] The average particle diameter of YA 2 03 powder (average particle diameter of ΑΑΙ02 03 powder (j ^ m) heat treatment temperature CC) peak intensity ratio YAL (420) / YAG (420 ) Peeling strength MPa There is cracking — Γ〇 ,,,,, and corrosion resistance test weight increase mg / hr B1 0.1 0.1 ~ 1500 ~ 0.000 3 Yes 07 B2 0.5 0.3 1500 0.206 43 m 0.0 B3 5 4 1500 0258 48 Μ 0.0 B4 20 20 1500 0.653 52 Μ 0.0 B5 50 50 1500 0.996 45 Μ 0.1 B6 80 80 1500 1.257 48 None 0.1 B7 100 100 1500 1.385 45 Μ 0.1 Βδ 120 120 H 1500 1.516 40 Μ 0.8 " B9 YA AG powder only (40 μττ1500 0.00 3 There is 1.0 It is known from Table 2 that in Example B9, no about titanite phase was found in the dissolution film. However, the peel strength is relatively low, cracks can be found, and the weight increase after the corrosion resistance test is also large. The spray-mixed powders in B1 ~ B8 have large peel strength and no cracks were found. Among them, in B 丨, the decrease in peel strength and cracks were observed after heat treatment. Especially if the oxidation age The particle size of the powder is set to 0.5 / zm ~ 100, and the alumina powder particles are When the diameter is set to 0.3 / zm to 100 // m, the peel strength will be very high above 400 MPa, and no cracking is observed. In B4 to B8, the peak strength of the yal phase after heat treatment will be Significant increase. This tendency is particularly evident in B 6, B 7, and B 8. In b 8, although the peak intensity is more than 1.5 than YAL (420) / YAG (420), no cracking or peeling is found. The strength does not decrease. However, the weight increase after the endurance will increase. This can be considered to be due to the difference in the crystalline phase of the film. As described above, according to the present invention, a kind of film can be provided to the substrate. The peeling strength of the oxide-shao oxide composite oxide film is relatively high.

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1232174

V. Description of the invention (21) (Bei test example c) Each component of the experimental examples c 1 to c 1 6 shown in Table I and Table 4 in Γ 1 λ. Among them, the trimmed, sintered body with a high quality oxide was polished with # 80 abrasive particles. A thickness of about 400 ㈣ is used to form a self-supporting film test of 150 0 V τ, 隹 —, and the average particle size of the YAG powder is 40 ° C at 1 60 0 ° C or by using # δ〇 仃 ^ 结. Sintered body. Then, each sintered body 2 is # 8. Grinding: Grinding and dressing are performed to form a self-supporting film test piece. CIn C16-, a solvent-ejecting film is formed on the basis of a length of 150 °, a width of 15 °, and a thickness of 5 ′, as in A. Then, the spray coatings obtained in Experiment 4 and C8 to 16 were heat-treated. For each test piece, the above-mentioned peak intensity ratio, peeling strength, presence or absence of cracks, corrosion resistance test results, porosity, surface area ratio (CM / g) of the rubidium adsorption method, average film thickness, α, mercury intrusion volume, Fine pore size and powder number.

The surface area ratio of the Kr method is the Kr gas adsorption multi-point bet method. The total area of the surface layer is set to 4 g / c m3. (Mercury squeeze-in volume, pore size) The mercury pore size porosimeter was used to measure the pore size in the range of 1 n m to 2 # 0 # m. Because the pores have a distribution ', Table 4 describes the diameter range in which the main peak exists. The surface tension of mercury is 485erg / cm2, and the contact angle is 130 °. (Porosity) Calculated by Archimedes' method. For C7 ~ C16, from the apparent specific gravity and the overall specific gravity obtained by the same method, it is confirmed that the pores are truly opened by gas.

7066-4891-PF (N); Tcshiau.ptd Page 25 1232174 V. Description of the invention (22) Hole. (Number of powder particles) 35 g of alumina powder used in Comparative Example C1 was suspended in 100 to 1000 cc of pure water, and then each sample of C1 to C16 was impregnated therein, and then in the air at 120 ° C Allow to dry. This operation is repeated until it becomes suspended ', whereby almost the entire amount is deposited on the test piece. With the surface coating side facing downward, a 50-cycle thermal cycle from room temperature to 200 ° C was applied, and the number of particles set on the lower Si wafer was counted. [Table 3] The average particle size of the young 203 powder (㈣ ai203) (the average particle diameter of the heat treatment (Am) heat treatment CC) Peak intensity ratio YAL (420) / YAG (420) peel strength (MPa) Cracked with or without C1 Comparative Example Sintered Oxidation Complex — 20 1S00t at ms 0 — No C2 Comparative Example Sintered YAG Punch Only YAG Powder (40 ym) isoot ms 0 — No C3 Comparative Example Sintered YAG YAG Only Powder (40 pm) 15001 ms 0 — No C4 Comparative Example YAG Synthetic Powder Discussion Only YAG Powder (Qing m) 1600 ^ 0 0 4 With C5 Lease Example Mixed Powder Spraying 20 20 Without Heat Treatment 0.243 10 Without C6 Lease example mix _ shot 20 20 without heat treatment 0.210 10 without C7 «example mix powder chain shot 20 20 without heat treatment 0.195 11 without C8« example mix _ shot 20 20 1400 0.597 23 without C9 «example mix _ shot 20 20 1400 0.541 19 No C10 example mixed powder shot 20 20 1400 0.553 30 No C11 «example mixed powder shot volume 20 20 1600 0 preparation 52 no C12 example mixed powder shot 20 20 1600 0.784 57 no C13 example mixed Powder training 20 20 1600 0.792 53 without C14 «Example mixed powder training 50 50 1600 0. 732 80 None C15 Rental Example Mixed Powder Shot 50 50 1600 0.718 62 None C16 Rental Example Mixed Shot 50 50 1600 0.696 87 None

7066-4891-PF (N); Tcshiau.ptd Page 26 1232174 V. Description of the invention (23) L less touch resistance test weight increase mg / hr porosity% average film thickness (_ table volume ratio a mercury squeezed volume _ Pore size range Number of particles C1 Comparative example 47 < 1 28 400 4 One majority C2 Comparative example 0.0 < 1 9 400 1 One more C3 Comparative example 1.3 10 9,317 400 1,491 0.08-2.5 Most C4 Comparative example 1.0 4 710 60 17 0.004-4 Most C5 examples 0.0 5 1,173 123 58 0.05-8 200 μC6 examples 0.0 6 1,191 212 101 0.05-8 50 C7 treasure examples 0.0 5 1J57 430 199 0.05-8 50 C8 examples 〇. &Quot; 〇11 1,256 99 50 0.05-8 0 C9 examples 0.0 13 1J92 196 33 0.05-8 10 C10 examples 0.0 13 1,183 408 193 0.05-8 0 C11 treasure examples 0.0 18 1,333 110 59 0.05-14 0 C12 examples 0.0 I 17 1,304 194 101 0.05-14 0 C13 賨 Examples 0.0 18 1,298 417 217, 0.05-14 0 C14 examples 0.0 17 1,382 111 61 0.2-20 0 C15 examples 0.0 16 1,370 220 121 02-20 0 C16 examples 0.0 16 1,404 406 228 02-20 0

Among Cl and C2, since they are dense sintered bodies, they have no fine powder holding ability. Most of the fine powders will fall from the sintered body onto the wafer. In C 3 'because YAG is insufficiently sintered', α becomes very large. This is due to insufficient sintering and the existence of most fine pores. This situation

Down 'After the heat cycle, the fine powder will drop most of them. In C 4, the surface layer α will become smaller and the fine powder will mostly fall. The so-called majority probably refers to "MO number / more. In c 5 to c 1 6 of the present invention, the suppression of fine powder on the wafer is particularly best among C8 to C16. It can be considered that the porosity is large sC5 to C7 Caused by Zhao. From the standpoint of peel strength, cu ~ Cl6 is particularly good. Ff In the examples of the invention, C5 ~ C16 are all mixed powders of yttrium oxide powder and Ming powder, which are dazzled to produce a dissolution film. In ⑵ ,

7066-4891-PF (N); Tcshiau.ptd Page 27 1232174 V. Description of the Invention (24) 6.7, because the heat treatment of the thermal spray film is not performed, the porosity is less than 10%. In C 8 to C 16, as a result of the heat treatment, the porosity will increase and exceed 10%. In addition, in experiments C5 to 16, the above-mentioned peak intensity ratio was in the range of 0.05 to 1.5, the peeling strength was high, and no crack was found. (Example C17) A talc with a particle size of 10 // m, fused quartz, and an alumina raw material with a particle size of 2 5 // m were kneaded with amidine cellulose and water to form a slurry. This paste was coated on an aluminum oxide substrate having a length of 160 mm, a width of 150 mm, and a thickness of 5 mm, such as C4 to C16, followed by a heat treatment in the air at 1,400 ° C. This step was repeated several times' to form an obsidian layer having an average thickness of 120 / zm. The overall density used to calculate the value of j is 2.0 g / cm3. The peeling strength was 36 M Pa 'and no crack was found. The weight resistance test increased by -0.3 mg / hour. The porosity is 21%. The average film thickness is 120 // m. Alpha value 1 3 9. Mercury was squeezed into a volume of 0.12 c c / g. Fine pore size range 1-4 0 // m. 0 fine particles. (Example C18) In the case of diamond, the substrate was set to silicon nitride. The production method is to add αmole silicon nitride powder with a particle size of about 1 // m, add 5mol% of Ya2O3 and 5mol0 / 〇 / 3 of silicon nitride, and mix them in a nitrogen atmosphere at 1 Dense sensitization at 8 5 0 ° C. The shape of the substrate is like C1 7. On this substrate, a diamond film with a thickness of about 50 m is formed by a / microwave CVD method. Quartz glass is arranged around the substrate, and Si and oxygen are mixed in the diamond film. Next, set the temperature of the substrate in the range of 150 to 300 ° C and expose it to a mixture of NF3 + Ar gas.

7066-4891-PF (N); Tcshiau.ptd Page 28 1232174__ V. Description of the invention (25) The pore structure was formed in the flow plasma for 10 hours. For the calculation of the alpha value, the overall density is 2.0 g / cm3. The peeling strength was 14 MPa, and no crack was found. The weight of the corrosion test was increased by ^ plus 0.0 mg / hour. The porosity is 10%. The average film thickness is 5 0 // m. Alpha value 5 3. 0 fine particles. As described above, according to the present invention, the deposit can be firmly held on the surface, thereby providing a low-particle structure which is less prone to generate fine powder due to the deposit.

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Claims (1)

91114037? 3 Mou f 3 Μ π 91114037? 3 Mou f 3 Μ π Application for patent scope 1. Manufacturing method of six kinds of yttrium oxide-alumina composite oxide film 1 Characterized by radon oxygen: a mixture of yttrium powder and ytterbium oxide The powder is sprayed on the body to form a soil film composed of yttrium oxide-alumina composite oxide.耵 2 · If the method of item i of the patent scope is applied, the average particle size of 50% of 誃 in the basin is above 0 ″, below 100,…. Method: The average particle diameter of 50% of the aluminum powder in # is above 0.1 mm and below 100 / zm / 4. If the method according to item [2] or item 2 of the scope of patent application, the shot film is heat treated. t Μ5. If you apply for the scope of the patent application item 丨 or the 2nd period-Oxidation Yiming composite oxide system contains at least the stone right phase, in which the emulsification application patent 6? η-emulsification composite oxide film 'its It is characterized by being manufactured according to the method of item 1 or item 2 of the patent application. The method of applying the third item in the patent application No. 7 method is to apply the method of the 8th item to the dissolution film, wherein the oxidation-oxidation-cutting method includes the garnet phase. < »Application No. 9: Composite oxide film, which is characterized by being prepared according to the method of item 8 of the conjugate. The material film, the oxidation period of the 6th item in the application of i-H in the 11th-composite oxide oxidation /, τ wooden tool length d / zni in μ, camp 0 ί 11 l Taxi See ◦ • Ivm cracks. Material film, of which ^ 6 items, oxide i oxide composite oxide, ’alumina composite oxide film, including stone 1232174 _ 案 i 虎 91111437_ 年月 月 Chromium_ 6. The scope of patent application for the garnet phase and perovskite phase, and the peak intensity YAL of the (420) plane of the perovskite phase obtained by X-ray diffraction measurement 420), and the ratio YAL (42 0) / YAG (42 0) to the peak intensity YAG (420) of the (420) plane of the garnet phase is not less than 0.5 and not more than 1.5. 1 2. The yttrium oxide-alumina composite oxide film according to item 10 of the scope of the application patent, wherein the yttrium oxide-alumina composite oxide film includes a stone right phase and a titania phase, and is subjected to X The ratio of the peak intensity of the (420) plane of the aluminite phase to the peak intensity of the (420) plane obtained by line diffraction measurement is 0 to the peak intensity of the (42) plane of the garnet phase. (42 0) / ¥ person 6 (420) is 0.05 or more and 1 · 5 or less. 1 3 · A yttrium oxide-alumina composite oxide film, comprising: a yttrium oxide-alumina composite oxide of a stone right phase; and an oxidation record of a perovskite phase-alumina composite oxide; and The ratio YAL (420) / YAG of the peak intensity yAL (420) of the (420) plane of the lacinite phase to the peak intensity (YAGU20) of the (42〇) plane of the garnet phase obtained by X-ray diffraction measurement. (420) is 0.05 or more and ι · 5 or less. 14. The yttrium oxide-alumina composite oxide film 'according to item 13 of the scope of patent application, wherein there is no crack with a length of 3 # m or more and a width of 0.1 / zm or more. 1 5. If the yttrium oxide-alumina composite oxide film of item 丨 3 or item 4 of the scope of patent application is applied, it is formed by the spray method. 16. A type of dissolution film, which is characterized by a dissolution film composed of yttrium oxide-alumina composite oxygen, without cracks in a length of 3 and a width of 0. 17 · The thermal spray film according to item 16 of the application, wherein the yttria- 1232174 Amendment No. 91114037 I. VI. Patent application scope The oxide oxide composite oxide system contains a garnet phase and a perovskite phase, and the (4 2 0) plane of the perovskite phase is obtained by X-ray diffraction measurement. The peak intensity YAL (420), and the ratio of the life value intensity yag (42〇) of the (420) face of the stone right stone to 420) Eight people 0 (420) is above 0.05 and 15 the following. 18. A corrosion-resistant member, comprising: a substrate and a corrosion-resistant member of a yttrium oxide-alumina composite oxide film, wherein the yttrium-alumina composite oxide film system includes a garnet phase Wash the perovskite phase, and obtain the peak intensity YAL (420) of the perovskite phase (42 °) / plane by X-ray diffraction measurement, and the peak intensity YAGU20 of the (42〇) plane of the garnet phase ) The ratio YAl (420) / YAG (42) is not less than 0.05 and not more than 15. · 19. For example, the corrosion-resistant member of the scope of patent application No. 18, which has cracks of 3 # m or more in length and width. /, 苴 by the two as stated in the scope of the 18th or 19th range of the refractory components, ^. "Emulsified Fei oxide composite oxide film is shaped by dissolution method 2: if the corrosion resistance of item 18 or 19 of the scope of patent application is applied, where the oxidation period-oxygen is described above, τWOMPa or more. Compound 5 Emulsification The glass strength of the film to the substrate is 22, such as the surname-resistant yttrium-alumina composite porphyrin, and T 4 emulsion. The emulsion film has a glass strength of 10 MPa to the substrate. ^ + 23 · A corrosion-resistant member, which is characterized by a corrosion-resistant member with an aesthetic film, in which the earth melting τ θ 蝽 film is made of yttrium-aluminum oxide, page 33, 7066-4891-PFl ( N) .ptc 1232174 Tea No. 91114 resembles a turtle turtle oxide above the scope of the patent application, and does not have a length of more than 3 // m and a width of 0.1 "claw cracks. 24. The corrosion-resistant member according to item 23 of the patent application range, wherein the yttrium oxide-alumina composite oxide system includes a garnet phase and a perovskite phase, and the perovskite is obtained by X-ray diffraction measurement The peak intensity YAL (420) of the (4 2 0) plane of the mineral phase, and the ratio YAL (420) / YAG (420) to the peak intensity yag (42 0) of the (42 0) plane of the garnet phase are at 0 · 05 or more, and ι · 5 or less. 25 ^ The corrosion-resistant member according to item 23 or item 24 of the scope of patent application, wherein the yttrium oxide-alumina composite oxide film is 10 MPa or more to the glass of the substrate. 26. If any one of items 18, 19, 23, and 24 of the scope of application for a patent, it is a surplus-resistant member that can be exposed to a pixel gas or a pixel gas. It can be exposed. It can be exposed. 27. For example, the corrosion-resistant member of the patent application No. 20, the corrosion-resistant member exposed in the tooth gas or plasma gas plasma ^ 28. Corrosion-resistant components according to item 21, which can be exposed to _ prime gas or _ prime gas electro-polymerization • 29 · M, please refer to the green scope of the patent scope _ plain rolling body or _ prime gas f slurry Nai Zesheng's "low-particle member" is characterized by having a low-grain member on the surface layer of the body, and the soil body: The α calculated by the formula is 50 or more and 70 or less. · «Second (according to the adsorption method) (under U 0 U, (cmh yf 矣 麻 麻, / go surface area ratio (Cm2 / g)) X (surface acoustic noise Um)) X (overall surface layer Density (g / cM)) 1232174 t No. 911] 1 of the scope of the patent application, wherein the surface layer is composed of a group of oxides, carbides, nitrogen 3 rare earth element oxides, solidified bodies including test soil, and mixtures, etc. Gases' chlorides, alloys, etc. The material selected in the 4 groups is composed of 31. · As for the patent application, the porosity is more than 10% by volume. The Ί member, of which the surface layer is 32. As the application for patent 丄: the following. The open porosity of the surface layer is a component of the closed air ", or the item of item 31, in which the rate) is 10 or more. / 、 Ratio of milk porosity (open porosity / closed porosity 3 3 · As the main door of the patent application 簕 surface layer 5 ^ the 30th or 31st member of the perimeter 34. The pore size of Rushen is U5 ~ 5 ”m The thickness of the surface layer; the surface layer or the surface layer, such as the 30th or 31st in the scope of the patent application, is composed of yttrium-containing materials, X Ang 6 i 孭 member M 1 + composition. The surface layer contains 37 · As applied to the aluminum oxide 稷 a oxide 0 low particle components can expose the 30th or 31st component of the rail, which is more than the material of the surface layer ^ ^, etch The material of the base material is the phase ratio. The component that has a large etching speed for the corrosive material (item 36 of the patent scope), where the low susceptibility is exposed to the corrosive low Below the material of the particle facet layer, the material of the base material has a larger erosive year to the corrosive substance compared to the table, which is # 7066-4891-PFl (N) .ptc Page 35 1232174 VI. Patent application scope No. 91114037 Amendment The germ line is a component of the 3-9% / ^^^ / 38 item, wherein the rotten silver substance is a milk body or a halogen gas plasma. The base ^ is composed of a member surrounding item f3Q or item 31, in which the composite oxide is composed of materials such as aluminum, spinel, yttrium oxide, zirconium, or these four materials. Select from the heart: special =: the first component, where the substrate is made of materials such as: Emulsification, Wrong, or these composite oxidation by Li 4 use 2 · will "Please patent No. 35 The component of the item 'where the surface layer is used, and the powder is mixed, and the mixed powder of powder and alumina powder is dissolved and sprayed on the base film. The member of the scope item 41, wherein the surface layer system is a mixed powder of yttrium yttrium powder and alumina powder is sprayed on the matrix =. The formed oxide 44 is composed of a homogeneous oxide of oxidized t. The 50% average particle size at the end of item 41 of the patent application range is more than or equal to 0, 〇__ the second element of the second powder If the item of the 44th scope of the patent 'where the 5 (U average) of the oxide powder The particle size is 0.1 or more and 100 or less. 46. If the structure in the scope of the application for the patent No. 44 is subjected to heat treatment,, A is a film system 47. If the structure in the scope of the 44 application for the patent, This yttrium oxide-oxide complex 5 oxide system contains at least a garnet phase. 7066-4891-PFl (N) .pt p. 36 1232174 48 • As the component of the 47th patent in Shengu's patent, the aluminum oxide composite oxide system contains the right rs such as the life force τ 〒 the emulsification period-milk. 3 There are garnet phase and perovskite phase, and the X-ray Ratio of the peak intensity of the (42 2) plane of the perovskite phase, YAU 42 0 below) to the peak intensity Y ^ G (42〇) of the (42 0) plane of the garnet phase, obtained by diffraction measurement. YAL (420) / YAG (420) is above 0.05, and again Page 37